Relativistic effects on NMR parameters of halogen-bonded complexes

Relativistic effects are found to be important for the estimation of NMR parameters in halogen-bonded complexes, mainly when they involve the heavier elements, iodine and astatine. A detailed study of 60 binary complexes formed between dihalogen molecules (XY with X, Y = F, Cl, Br, I and At) and fou...

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Detalles Bibliográficos
Autores: Alkorta, Ibon, Elguero, José, Yáñez Montero, Manuel, Mo Romero, Otilia, Montero Campillo, M. Merced
Tipo de recurso: artículo
Fecha de publicación:2019
País:España
Institución:Universidad Autónoma de Madrid
Repositorio:Biblos-e Archivo. Repositorio Institucional de la UAM
Idioma:inglés
OAI Identifier:oai:repositorio.uam.es:10486/718882
Acceso en línea:http://hdl.handle.net/10486/718882
https://dx.doi.org/10.3390/molecules24234399
Access Level:acceso abierto
Palabra clave:Halogen bonding
astatine
relativistic effects
NMR
absolute shieldings
nuclear quadrupolar coupling constants
Química
Descripción
Sumario:Relativistic effects are found to be important for the estimation of NMR parameters in halogen-bonded complexes, mainly when they involve the heavier elements, iodine and astatine. A detailed study of 60 binary complexes formed between dihalogen molecules (XY with X, Y = F, Cl, Br, I and At) and four Lewis bases (NH3, H2O, PH3 and SH2) was carried out at the MP2/aug-cc-pVTZ/aug-cc-pVTZ-PP computational level to show the extent of these e ects. The NMR parameters (shielding and nuclear quadrupolar coupling constants) were computed using the relativistic Hamiltonian ZORA and compared to the values obtained with a non-relativistic Hamiltonian. The results show a mixture of the importance of the relativistic corrections as both the size of the halogen atom and the proximity of this atom to the basic site of the Lewis base increase